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Biomass and Bioenergy: Research Paper
Biomass and Bioenergy: Research Paper
Research paper
Keywords: Municipal solid waste (MSW) contains on an average 40% food waste and needs to be managed in an en-
Food waste vironment friendly manner. Food wastes have high energy content and offer a good potential feed stock for
Microwave pyrolysis pyrolysis. Microwave assisted pyrolysis of food waste at different microwave power levels has been carried out in
Bio-oil the present study. Maximum bio-oil yield of 30.24 wt.% is obtained under the optimized pyrolysis conditions of
Optimization and response surface
400 °C temperature, 30 min residence time and 50 mL min-1 of nitrogen flow rate at the microwave power of
methodology
450 W. The regression model with 95% confidence level resulted in the high value of R2 = 95.4% with R2
adjusted = 91.2% indicates a very good or excellent fit of the data to the model. Main functional groups as
detected by the Fourier transform infrared (FTIR) analysis are alcohols, alkenes, aromatic compounds, primary
and secondary amines, carboxylic acid, esters and phenols. Oxygenated and non oxygenated compounds, ni-
trogenated compounds and other compounds such as phosphine, methyl-, propane, 2-fluoro-, (2-hydroxyethyl)
trimethylsilyl methyl sulfide, and 1,3-bis(2-hydroxymethyl)urea have been identified by the gas chromato-
graphy/mass spectrometry (GC-MS) analysis. The heating value of the bio-oil was 23.94 MJ kg−1.
1. Introduction corn stover was carried out in a pressurized batch reactor at different
temperatures. Increase in the temperature resulted in the decrease of
The global demand for energy is increasing at a faster rate due to the biochar yield but increase in the gas yield was observed. The yields of
rapid growth in the world's population and day to day development of biochar (37.3 wt %) and bio-liquid (31.4 wt %) were maximum at a
new service, commercial and industrial sectors. At the same time, en- temperature of 400 °C where as the gas yield (21.2 wt %) was maximum
ergy resources which are fulfilling our everyday energy requirements at 600 °C. Effects operating parameters such as temperature
are depleting at an unpredictable manner. In this regard biomass has (400–550 °C), heating rate (7–40 °C min−1) and nitrogen flow rate
been recognized as a major renewable energy source to supplement (50–200 cm3 min-1) on the pyrolysis of corncob in a fixed bed reactor
declining fossil fuel resources [1–5]. were investigated experimentally by Demiral et al. [4]. Bio-oil yield of
Abnisa et al. [1] have investigated the possibilities of palm shell as a 26.44 wt % was obtained at an operating temperature of 500 °C with a
source of biomass energy in Malaysia by pyrolysis. Bio-oil yield of heating rate of 40 °C min−1 and inert gas flow rate of 100 cm3 min-1
47.3 wt.% was obtained by the pyrolysis of palm shells in a fluidized- respectively. The main contents of the bio-oil were aliphatic, aromatic
bed reactor with an operating temperature of 500 °C, nitrogen flow rate hydrocarbons and oxygenated species such as such as carboxyl and
of 2 L min-1 and 60 min reaction time. Oxygen content of the bio-oil was carbonyl groups. The heating value of the bio-oil was 26.22 MJ kg−1.
71.40 wt.% that has required upgradation prior to industrial applica- Özçimen and Karaosmanoglu [5] have reported the characteristics of
tions. Effect of pyrolysis temperature on the characteristics of pyrolyzed biofuels obtained by the cold extraction pressing of rapeseed cake. Bio-
Canadian waste biomass was reported by Azargohar et al. [2]. Pyrolysis oil and biochar were rich in carbon with higher amounts of fixed carbon
experiments were performed by using a mobile pyrolysis unit in the and ash content, but lower amounts of volatile matter than rapeseed
temperature range from 400 to 550 °C. Development of aromatic cake. Heating values of the bio-oil and biochar were of 36.4 and 25.3
structure in bio-char samples was observed at higher temperatures. MJ kg−1 respectively. Biofuels obtained in this study were relatively
Production potential of bio-fuels by the pyrolysis of corn stover was pollution-free and an environmental friendly fuels.
studied experimentally by Capunitan and Capareda [3]. Pyrolysis of Around 1.3 billion tons of food is wasted globally every year though
∗
Corresponding author.
E-mail address: rajmohanbala@gmail.com (B. Raj Mohan).
https://doi.org/10.1016/j.biombioe.2019.01.014
Received 23 June 2018; Received in revised form 29 November 2018; Accepted 21 January 2019
Available online 19 February 2019
0961-9534/ © 2019 Elsevier Ltd. All rights reserved.
H.M. Kadlimatti, et al. Biomass and Bioenergy 123 (2019) 25–33
Table 1
Proximate analysis, ultimate analysis and heating values of FWS.
Proximate analysis (wt. %) Ultimate analysis (wt. %) Heating values (MJ kg-1)
a,b
by difference.
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H.M. Kadlimatti, et al. Biomass and Bioenergy 123 (2019) 25–33
Table 2
Central composite design matrix for process optimization.
Run order Std order Coded factors Actual factors Actual yield (wt. %) Predicted yield (wt. %)
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H.M. Kadlimatti, et al. Biomass and Bioenergy 123 (2019) 25–33
experimental yields of bio-oil is presented in Table 2. Model terms were are provided in Table 3 and Table 4. The model value of F (22.92)
rejected or selected based on the value of P with 95% confidence level. indicated that, the model was statistically valid and significant. Higher
Results were analyzed by using analysis of variance (ANNOVA) ob- F value for linear (7.50) and square (60.33) with lower values of P
tained from minitab software (Version 14; Minitab Ltd. Coventry CV suggests that the linear and square terms were significant. However
32 TE, UK). Minitab software includes experimental design, data ana- lower value of F for interaction (0.94) with a higher value of P (0.456)
lysis, quadratic model, and response surface graphs. Effects of operating indicated that, the interaction terms were not having significant effect
parameters on the pyrolysis yield were studied by using response sur- on the bio-oil yield. Higher F-value of lack-of-fit and the lower prob-
face graphs. ability (P) values of the parameters involved suggest that, the model
terms were significant.
2.4. Analysis of bio-oil
Bio-oil obtained under the optimum pyrolysis condition was used 3.2. Effect of operating variables on bio-oil yield
for the analysis. Proximate and ultimate analysis of the bio-oil was
carried out as per ASTM standard methods mentioned in section 2.1. The effect of operating parameters namely temperature, time and
The HHV and LHV of the bio-oil were calculated by using Eq. (1) and nitrogen flow rate on the bio-oil yield were found by using RSM. Effects
Eq. (2) [1]. Heating values were also determined experimentally by these operating parameters were represented in the form of three di-
using bomb calorimeter. Density of the bio-oil was calculated by spe- mensional surface and contour plots from Figs. 2-3. It is evident from
cific gravity method and pH value was calculated by using calibrated the regression coefficients (Table 3) that, both the temperature and
digital pH meter (Equiptronics-EQ-610, India) at a room temperature of time were considered as most significant parameters to effect bio-oil
30 °C. Viscosity of the bio-oil was calculated as per ASTM standard production due to lower values of P. Nitrogen flow rate was considered
methods D 445 and D 2515 by using Cannon-Fenske viscometer at a as less significant to effect pyrolysis process due to higher value of P
room temperature of 30 °C. Water content of the bio-oil was measured though it was having positive effect, as observed from Eq. (7), that has
by using Carl-Fischer 899 Coulometer from Metrohm. FTIR spectrum of increased the bio-oil yield.
the bio-oil to know the functional groups was carried out by using a Mushtaq et al. [22] reported that, an increase in the nitrogen flow
FTIR analyzer (Bruker Alpha-400, Germany) and GC-MS (Jeol-JMS- rate reduces the final pyrolysis reaction temperature as the heat carried
T100GCV, AccuTopGCV, Japan) analysis was carried out at the So- by the carrier gas is more than that of the heat released by the surface
phisticated Instrument Analysis Facility (SAIF), Indian Institute of carbon solids of the upper biomass layer. Heat generated by the upper
Technology Bombay, Mumbai, India. carbon particles, bottom layer FWP and heat carried with nitrogen
reached equilibrium at 50 mLmin-1 and resulted in the maximum bio-oil
3. Results and discussion yield. Bio-oil yield was decreased beyond 50 mLmin-1 nitrogen flow rate
that has affected the optimum pyrolysis temperature [23]. This effect is
3.1. Statistical analysis of bio-oil model shown in the response surface and contour graphs (Fig. 2b, c, Fig. 3b
and c). Among the variables investigated in this study, both tempera-
The actual values of the operating parameters namely temperature, ture and time were having their effect to enhance the bio-oil yield
time and nitrogen flow rate and the response, which is the bio-oil, yield, (Fig. 2a, c, Fig. 3a and c). Açıkalın et al. [24] reported that, the bio-oil
for twenty experiments were used for the prediction of bio-oil model. yield increases till optimum pyrolysis temperature and decreases be-
The regression model with 95% confidence level resulted in the high yond the optimum pyrolysis temperature due to secondary reactions
value of R2 = 95.4% with R2 adjusted = 91.2% indicated a very good thereby increasing the gas yield with increase in temperature. Increase
or excellent fit of the data to the model. Similar results were observed in the reaction temperature (400 °C) and time (30 min) resulted in the
with the other biomass feed stock materials [1,17,20,21]. The basic removal of volatiles causing an increase in the bio-oil yield (30.24 wt
approach to fit the collected experimental data with the empirical %) as the pyrolysis process was an endothermic process (Figs. 2 and 3).
model is the regression analysis. The response (bio-oil yield) and vari- On the other hand increase in the operating parameters beyond the
ables involved were fitted to each other by multiple regressions in this optimum conditions resulted in the decrease of bio-oil yield and in-
study [19]. The final bio-oil model in terms of the coded values is given crease in the gas yield due to production of low molecular weight
by Eq. (7). Where YBOY is the bio-oil yield (wt. %), A is the temperature compounds, involving secondary cracking of vapours in to incon-
(°C), B is the time (min) and C is the nitrogen flow rate (mLmin−1). It is densable gases [24–26] and faster pushing of the incondensable gases
evident from Eq. (7) that, the linear terms such as temperature, time due to increased flow of nitrogen gas, as it was used as a carrier gas
and nitrogen flow rate were having the positive effect to increase the (Fig. 2a and c). Uniform heating of biomass sample from core to sur-
bio-oil yield when these variables are increased, whereas, square terms face, which is the characteristics of microwaves, at 450 W resulted in
were having negative effect and decreased the bio-oil yield. the temperature required for the secondary cracking of vapours in to
The estimated regression coefficients and ANNOVA for bio-oil yield incondensable gases [17,27].
Table 3
Estimated regression coefficients for bio-oil yield (%).
Term Coefficient SE Coefficient T P Remarks
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H.M. Kadlimatti, et al. Biomass and Bioenergy 123 (2019) 25–33
Table 4
Analysis of variance for bio-oil yield (%).
Source Degrees of freedom Sequential sum of squares Adj SS Adj MS F P Remarks
Total 19 377.40
Fig. 2. Surface plots of bio-oil yield (%) at 450 W (a) temperature (°C) vs. time (min.), (b) temperature (°C) vs. nitrogen flow rate (mLmin−1) and (c) time (min) vs.
nitrogen flow rate (mLmin−1).
Fig. 3. Contour plots of bio-oil yield (%) at 450 W (a) time (min) vs. tem- Fig. 4. Comparision between actual and predicted yields of bio-oil.
perature (°C), (b) nitrogen flow rate (mLmin−1) vs. temperature (°C) and (c)
nitrogen flow rate (mLmin−1) vs. time (min).
29
H.M. Kadlimatti, et al. Biomass and Bioenergy 123 (2019) 25–33
Fig. 5. FTIR spectra of bio-oil derived from food waste at 400 °C temperature, 30 min time and 50 mLmin-1 of nitrogen flow rate at a power level of 450 W.
3.3. Optimization by response surface modeling or “oop” band that point out the difference between aromatics and
organic compounds without an aromatic ring was observed between
Optimum pyrolysis parameters those can maximize the bio-oil yield 675 cm−1 and 900 cm−1 and this was noticed at 868.99 cm−1. Similar
were investigated by developing a mathematical model equation using to the other organic compounds a C-H methyl rock stretching vibration
RSM. Maximum bio-oil yield of 30.24 wt % was obtained at the pyr- was observed at 1384.49 cm−1. The N-H stretching vibrations between
olysis conditions of 400 °C temperature, 30 min time, and 50 mLmin-1 3300 cm−1 and 3400 cm−1 indicated the presence of weak secondary
of nitrogen flow rate at a power level of 450 W. The predicted value of amines. The N-H bending vibration of primary amines was observed
the bio-oil yield was 0.02 wt % less than the experimental value. The between 1580 cm−1 and 1650 cm−1. The C-N stretches of aromatic
comparison between the experimental and predicted values was carried amines (1272.74 cm−1) were observed in the region from 1250 to
out under the same pyrolysis conditions. Accuracy of the bio-oil model 1335 cm−1, whereas, the aliphatic amines (1084.41 cm−1 and
obtained was verified by conducting a number of experiments under the 1129.60 cm−1) were observed in the region between 1020 cm−1 and
similar pyrolysis conditions. The relationship between the predicted 1250 cm−1 respectively. Another strong broad band representing the
bio-oil yields using Eq. (7) and the experimental values is shown in primary and secondary amines is N-H wag band (665–910 cm−1) which
Fig. 4. It is evident from Fig. 4 that, the experimental values were very was identified at 868.99 cm−1. The N-O symmetric stretching vibration
close to that of the predicted values. (normally observed at 1365 cm−1)) of nitroalkanes was observed at
1384.49 cm−1. FTIR analysis of the bio-oil was similar to the other
3.4. Physical and chemical characterization of bio-oil biomass feedstock materials [1,4].
GC-MS analysis was carried out to find the major compounds pre-
3.4.1. Chemical composition of bio-oil sent in the bio-oil. GC-MS analysis identified 11 major compounds out
Bio-oil obtained under the optimum pyrolysis conditions of 400 °C of more than 500 compounds those were present in the bio-oil. The
temperature, 30 min time and 50 mLmin-1 of nitrogen flow rate at a major identified chemical compounds of the bio-oil along with their
power level of 450 W was used for the analysis of chemical composi- molecular formula, molecular weight, structure and peak area (%) are
tion. The FTIR spectra of bio-oil obtained from the microwave pyrolysis shown in Table 5. Compounds such as oxygenated and non oxygenated
of FWP is shown in Fig. 5. The bio-oil obtained in this study contains compounds, nitrogenated compounds and other compounds such as
more water that was responsible for the peaks of the FTIR [28,29]. The phosphine, methyl-, propane, 2-fluoro-, (2-hydroxyethyl) trimethylsilyl
C-O stretch of alcohols was observed in the region from 1050 to methyl sulfide, and 1,3-bis (2-hydroxymethyl) urea were identified by
1260 cm−1 where as the C-O stretches of esters were observed between the GC-MS analysis. Identified chemical compounds were having the
1000 cm−1and 1300 cm−1. The C-C stretching vibrations between carbon distribution in the range between C and C6 with molecular
1640 cm−1 and 1680 cm−1 shows the presence of alkenes. Week bands, weight varying from 48 to 164. It can be seen from Table 5 that, the
commonly observed in most of the aromatic compounds, in the region phosphine, methyl-was the compound with lower molecular weight of
from 1000 to 250 cm−1 were due to C-H in-plane bending. Out of plane 48 with the largest peak area of 97.6%, whereas, (2-hydroxyethyl)
30
H.M. Kadlimatti, et al. Biomass and Bioenergy 123 (2019) 25–33
Table 5
Major identified chemical compounds of bio-oil by GC-MS.
Sl. No Retention time (min.) Chemical compounds Molecular formula Molecular weight Structure Area (%)
trimethylsilyl methyl sulfide was having the higher molecular weight of to non oxygenated compounds such as phosphine, methyl-, propane, 2-
164 with a peak area of 14.2%. Among the identified compounds, the fluoro-, thioimidodicarbonic diamide and carbonothioic dihydrazide.
amines group was the largest group compared to the other chemical Presence of alcohol was detected in the FTIR analysis, but not detected
compounds. Minimum peak area of 10.1% was observed with 1, 3-bis by the GC-MS analysis due to thermal instability of the bio-oil [1] and
(2-hydroxymethyl) urea with a retention time of 32.5 min having a storage of bio-oil till the GC-MS analysis. The sulfur which was not
molecular weight of 120. Oxygenated compounds such as 2-pyrrolidi- detected during the elemental analysis, probably due to the very low
none, 2-ethoxyethylamine, ethanamine, 2-methoxy-, acetic acid, mer- percentage, was detected by GC-MS analysis and appeared in the bio-oil
capto-, l-cysteine, (2-hydroxyethyl) trimethylsilyl methyl sulfide and as (2-hydroxyethyl) trimethylsilyl methyl sulfide with a peak area of
1,3-bis(2-hydroxymethyl) urea were dominant in the bio-oil compared 14.2%.
31
H.M. Kadlimatti, et al. Biomass and Bioenergy 123 (2019) 25–33
higher than that, calculated by using Eq. (1), as the latter did not in- functional groups identified by FTIR analysis were alcohols, phenols,
clude the dissociation effects. HHV, LHV, and heating value of the bio- carboxylic acid, alkenes, aromatic compounds, primary, secondary and
oil as determined by the bomb calorimeter were close to that of FWS. aliphatic amines and nitroalkanes respectively. Compounds such as
This was mainly due to the loss of some higher heating value hydro- oxygenated and non oxygenated compounds, nitrogenated compounds
carbons [23]. and other compounds with phosphine, methyl-, propane, 2-fluoro-, (2-
hydroxyethyl) trimethylsilyl methyl sulfide and 1, 3-bis (2-hydro-
4. Practical applications and future research prospects xymethyl) urea were identified by GC-MS analysis. Bio-oil obtained in
this study cannot be used as a bio-fuel, as it contains more water as well
Microwave assisted pyrolysis is an efficient and effective method of as nitrogenated compounds. However, bio-oil obtained can be upgraded
waste disposal along with the recovery of value added products like bio- and blended with diesel to use as a fuel through further investigation.
oil, biochar and biogas. Future research focusing on chemical reaction Land filling of food waste is known to cause leachate formation, me-
kinetics, exergy analysis, co-pyrolysis by blending food waste with thane gas production, bad odour and health related problems. Hence,
other biowastes, catalyst based pyrolysis to obtain enhanced bio-oil the thermal treatment of food waste using microwaves with short
yield, effect of FWP size on bio-oil yield and cost benefit analysis may period of time provides the best way of carbon sequestration through
be undertaken. carbon neutral cycle. Recovery of valuable chemicals from the bio-oil,
as an example a variety of pharmaceutical drugs are derivatives of 2-
5. Conclusion pyrrolidinone, using suitable separation technology appears to be the
highlight of this work. Solid residue obtained under the optimum pyr-
Optimum conditions to produce bio-oil by the pyrolysis of food olysis conditions can be used for heating applications.
waste using response surface methodology were investigated in this
study. Bio-oil model was built using experimental data and ANOVA. Acknowledgement
Temperature and time were the most effective parameters to effect bio-
oil production, whereas the nitrogen flow rate and interaction terms First Author gratefully acknowledge the National Institute of
were less significant parameters. Bio-oil yield of 30.24 wt % was ob- Technology Karnataka Surathkal, India for the financial support to
tained at the pyrolysis conditions of 400 °C temperature, 30 min time, purchase microwave reactor under the annual plan fund No: 233/
and 50 mL min-1 of nitrogen flow rate at a power level of 450 W. The NITK/CHE/APF/2014-15/A9 dated 23-02-2015.
Appendix A
HHV
MJ
=
338.2 × C + 1442.8 × H ( O
8 )
kg 1000 (1)
MJ
LHV = HHV (0.218 × H )
kg (2)
= (2n)1/4 (3)
N = 2n + 2n + nc (4)
YBOY = 30.22 + 1.12A + 1.26B + 0.13C 3.08A2 1.69B2 3.64C 2 0.08AB + 0.48AC + 0.61BC (7)
32
H.M. Kadlimatti, et al. Biomass and Bioenergy 123 (2019) 25–33
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